CN109517538B - Adhesive and preparation method thereof, and flexible copper-clad plate and preparation method thereof - Google Patents

Adhesive and preparation method thereof, and flexible copper-clad plate and preparation method thereof Download PDF

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CN109517538B
CN109517538B CN201811401832.9A CN201811401832A CN109517538B CN 109517538 B CN109517538 B CN 109517538B CN 201811401832 A CN201811401832 A CN 201811401832A CN 109517538 B CN109517538 B CN 109517538B
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adhesive
component
temperature
layer
parts
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CN109517538A (en
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李政
盘冠华
何志球
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Guangdong Leary New Materials Technology Co ltd
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Guangdong Leary New Materials Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J127/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Adhesives based on derivatives of such polymers
    • C09J127/02—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J127/12—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Adhesives based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C09J127/18—Homopolymers or copolymers of tetrafluoroethene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/085—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/088—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/09—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B32B27/322—Layered products comprising a layer of synthetic resin comprising polyolefins comprising halogenated polyolefins, e.g. PTFE
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/0008—Electrical discharge treatment, e.g. corona, plasma treatment; wave energy or particle radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/0012—Mechanical treatment, e.g. roughening, deforming, stretching
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/16—Drying; Softening; Cleaning
    • B32B38/162—Cleaning
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J109/00—Adhesives based on homopolymers or copolymers of conjugated diene hydrocarbons
    • C09J109/02—Copolymers with acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J109/00—Adhesives based on homopolymers or copolymers of conjugated diene hydrocarbons
    • C09J109/06—Copolymers with styrene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J127/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Adhesives based on derivatives of such polymers
    • C09J127/02—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J127/12—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Adhesives based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J127/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Adhesives based on derivatives of such polymers
    • C09J127/02—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J127/12—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Adhesives based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C09J127/16—Homopolymers or copolymers of vinylidene fluoride
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/0012—Mechanical treatment, e.g. roughening, deforming, stretching
    • B32B2038/0016—Abrading
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • C08K2003/2224—Magnesium hydroxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
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    • C08K2003/323—Ammonium polyphosphate
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K3/38—Boron-containing compounds
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Abstract

The invention provides an adhesive and a preparation method thereof, wherein the adhesive is formed by mixing a component A and a component B, and the component A comprises the following raw materials in parts by mass: 50-60 parts of fluorine-containing elastomer polymer, 20-40 parts of epoxy resin, 40-80 parts of organic solvent, 5-10 parts of environment-friendly flame-retardant filler, 1.5-5 parts of impact modifier, 0.5-1 part of silane coupling agent and 0.1-1 part of reaction promoter; the component B comprises the following raw materials in parts by mass: 2-4 parts of a curing agent and 2-10 parts of an organic solvent; the solid content ratio of the component A and the component B when mixed is 10: (0.2-0.4). The invention also provides a flexible copper-clad plate and a preparation method thereof, wherein the flexible copper-clad plate comprises a substrate layer, an adhesive layer and a copper foil layer, the adhesive layer is formed by coating the adhesive, and the substrate layer and the copper foil layer are bonded together by the adhesive layer. The product prepared by the invention has the characteristics of low dielectric constant, high weather resistance, high bending resistance, higher stability and longer service life.

Description

Adhesive and preparation method thereof, and flexible copper-clad plate and preparation method thereof
Technical Field
The invention relates to an adhesive and a preparation method thereof, a flexible copper-clad plate and a preparation method thereof, and belongs to the technical field of copper-clad plates.
Background
The IT industry is a core industry of high informatization, and the high frequency of electronic equipment in the IT industry is a developing trend, especially in the increasing development of wireless network and satellite communication, the high speed and high frequency of information products, and the standardization of voice, video and data of wireless transmission with large capacity and high speed of communication products. Therefore, the high frequency FPC (flexible circuit board) is required for the new generation of information products, and is inevitably developed rapidly in the next few years, and the demand for the high frequency FPC will rise greatly.
The soft copper-clad plate is used as one of the core materials of the FPC, and the soft copper-clad plate also tends to develop in the aspect of low dielectric property in the development of high frequency following the FPC. Meanwhile, in consideration of the development of novel high-frequency information equipment in recent years, the weather resistance of products is required to be improved more and more, for example, the products are applied to communication products such as satellite systems and high-frequency receiving base stations and outdoor transmission equipment in extreme environments, the weather resistance of the products is required to be higher, and the products have frequent dynamic functions, so that the high-frequency FPC bending resistance is required to be higher to a certain extent. Therefore, under the development trend of novel information products, the performance of the flexible copper-clad plate needs to have higher weather resistance and bending resistance on the basis of good basic performances such as low dielectric constant, low dielectric loss and the like in special environment and functional application. The flexible copper-clad plate prepared by the existing adhesive has the problems of high dielectric loss, unstable performance and short service life due to the poor high dielectric constant, weather resistance and bending resistance, and even seriously influences the service life and performance stability of the high-frequency FPC.
How to invent an adhesive, the flexible copper clad laminate prepared by the adhesive has the characteristics of low dielectric constant, high weather resistance, high bending resistance, higher stability and longer service life, and is a problem to be solved urgently by people in the technical field at present.
Disclosure of Invention
Aiming at the defects, the invention aims to provide the adhesive and the preparation method thereof, the flexible copper-clad plate and the preparation method thereof, and the prepared adhesive and the flexible copper-clad plate have the characteristics of low dielectric constant, high weather resistance, high bending resistance, higher stability and longer service life.
In order to achieve the purpose, the invention adopts the following technical scheme:
the adhesive is formed by mixing a component A and a component B, wherein the component A comprises the following raw materials in parts by mass: 50-60 parts of fluorine-containing elastomer polymer, 20-40 parts of epoxy resin, 40-80 parts of organic solvent, 5-10 parts of environment-friendly flame-retardant filler, 1.5-5 parts of impact modifier, 0.5-1 part of silane coupling agent and 0.1-1 part of reaction promoter;
the component B comprises the following raw materials in parts by mass: 2-4 parts of a curing agent and 2-10 parts of an organic solvent;
the solid content ratio of the component A to the component B when mixed is 10: (0.2-0.4).
Preferably, the fluorine-containing elastomer polymer is one or more of epoxy resin modified vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer, chlorotrifluoroethylene-vinylidene fluoride copolymer, polytetrafluoroethylene modified styrene-butadiene/nitrile rubber, vinylidene fluoride-tetrafluoroethylene-perfluoromethyl vinyl ether-vulcanization point monomer quadripolymer and tetrafluoroethylene-hydrocarbon propylene copolymer;
the epoxy resin is one or more of polyphenol type glycidyl ether epoxy resin, heterocyclic type glycidyl epoxy resin, organic titanium modified bisphenol A type epoxy resin, glycidyl amine type epoxy resin and aliphatic epoxidized olefin compound;
the environment-friendly flame-retardant filler is prepared by mixing a phosphorus flame retardant and an inorganic salt flame retardant in a proportion of 1: (1-3), wherein the phosphorus flame retardant is one or more of ammonium polyphosphate, hypophosphite, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, triphenyl phosphorus oxide, diethyl aluminum hypophosphite and resorcinol bis (2, 6-dimethylphenyl) phosphate; the inorganic salt flame retardant is one or more of aluminum hydroxide, magnesium hydroxide, zinc borate and silicate;
the impact modifier is one or more of chlorinated polyvinyl chloride, ethylene-vinyl acetate copolymer and 4, 5-epoxy tetrahydrophthalic dioctyl ester;
the silane coupling agent is one or more of gamma-glycidyl ether propyl trimethoxy silane, 3-glycidyl ether oxygen propyl triethoxy silane, 3-glycidyl ether oxygen propyl trimethoxy silane and 2- (3, 4-epoxy cyclohexyl) ethyl trimethoxy silane;
the reaction accelerator is one or more of organic urea, N' -diphenylguanidine, N-diethylaniline and 2,4, 6-tris (dimethylaminomethyl) phenol;
the curing agent is one or more of an amino resin crosslinking polycondensation-acrylate polymerization system curing agent, a dicyandiamide latent curing agent and a mixed polyisocyanate curing agent;
the organic solvent is one or more of butanone, acetone, cyclohexane, cyclohexanone, toluene, xylene and N, N-dimethylformamide.
The preparation method of the adhesive comprises the following steps:
(a) mixing a fluorine-containing elastomer polymer, epoxy resin and an organic solvent of the component A according to a formula amount, stirring at a constant temperature, adding a silane coupling agent according to the formula amount, and stirring at a reduced speed for 40-60 min to obtain a main agent of the component A;
(b) preparing an environment-friendly flame-retardant filler, adding an impact modifier and the environment-friendly flame-retardant filler into a component A main agent according to the formula amount, stirring for 60-90 min at the rotating speed of 1000-3000 rpm, adding a reaction promoter according to the formula amount after uniformly stirring, and stirring for 10-15 min at the rotating speed of 1000-3000 rpm to obtain a component A;
(c) mixing and dissolving a curing agent and an organic solvent of the component B according to the formula amount to obtain the component B;
(d) and mixing the component A and the component B according to a proportion, stirring for 30-40 min, and sieving to obtain the adhesive.
Preferably, in the step (a), the parameters of the constant-temperature stirring treatment are as follows: the temperature is one of 60-80 ℃, the rotating speed is 1000-1500 rpm, the time is 4h, the temperature of the constant-temperature stirring treatment is kept in the adding process of the silane coupling agent, and the rotating speed of the speed reduction stirring is 500-800 rpm.
Preferably, the stirring speed in the step (d) is 800-1500 rpm, and the sieve mesh number is 300-400 meshes.
The flexible copper-clad plate using the adhesive comprises a substrate layer, an adhesive layer and a copper foil layer, wherein the adhesive layer is formed by coating the adhesive, and the adhesive layer is used for bonding the substrate layer and the copper foil layer together.
Preferably, the substrate layer is a biaxially oriented substrate film, and the substrate film is one of a PI film, a PEFT film, a PEN film, and an Aramid film; the copper foil layer is electrolytic copper foil or rolled copper foil;
the thickness of the substrate layer is 15-110 μm; the thickness of the bonding layer is 5-70 μm; the thickness of the copper foil layer is 12-150 mu m.
A preparation method of the flexible copper-clad plate using the adhesive comprises the following steps:
(1) performing corona treatment on the surface of the base material layer;
(2) carrying out chemical cleaning and mechanical grinding treatment on the surface of the copper foil layer to enable the surface of the copper foil layer to be provided with a rough surface, so as to obtain a pretreated copper foil layer;
(3) coating an adhesive on the corona treatment surface of the substrate layer to enable the substrate layer to be provided with an adhesive layer, and drying to obtain the adhesive substrate layer;
(4) bonding the bonding surface of the bonding base material layer with the rough surface of the pretreated copper foil layer, carrying out normal-temperature roller pre-lamination, and then carrying out high-temperature hot roller lamination, wherein the temperature of the high-temperature hot roller lamination is set to be 110-150 ℃, so as to obtain a semi-finished product of the flexible copper-clad plate;
(5) and (4) after the soft copper-clad plate semi-finished product is unwound, performing staged curing treatment to obtain a soft copper-clad plate finished product.
Preferably, the corona value set in the corona treatment of the step (1) is greater than 52 dy; the speed of coating the adhesive in the step (3) is 2-10 m/min, and the temperature of drying treatment is 140-220 ℃.
Preferably, the step-wise aging treatment of step (5): the temperature is increased from 30 ℃ to 100 ℃ in 100min in the first stage; the second stage is to keep the temperature at 100 ℃ within 120 min; in the third stage, the temperature is increased from 100 ℃ to 150 ℃ within 180 min; the fourth stage is to maintain the temperature at 150 ℃ within 120 min; in the fifth stage, the temperature is increased from 150 ℃ to 180 ℃ within 120 min; the temperature dropped from 180 ℃ to 30 ℃ in the sixth stage within 60 min.
The invention has the beneficial effects that: (1) the core component of the adhesive is fluorine-containing elastomer polymer, so that the adhesive has good low dielectric property, medium resistance and non-combustibility, and effectively reduces the dielectric loss of the flexible copper-clad plate; the fluorine-containing elastomer polymer has excellent stability, and the base material layer and the copper foil layer which are bonded by the adhesive are perfectly attached, so that the flexible copper clad laminate has higher weather resistance; the fluorine-containing elastomer polymer has good elasticity and recoverability, and endows the flexible copper-clad plate with strong bending resistance and good deformation recovery capability; (2) the epoxy resin plays a role of a carrier in the adhesive, has good dielectricity, high and low temperature resistance, water absorption resistance and the like, can improve the stability and weather resistance of the required adhesive, has good impact toughness and bonding property, and can improve the adhesive force and impact property of the epoxy resin to the surface of a metal substrate when being mixed with the fluorine-containing elastomer polymer; (3) the silane coupling agent in the adhesive can react with the environment-friendly flame-retardant filler, so that the applicability and the dispersibility of the environment-friendly flame-retardant filler are improved; the fluorine-containing elastomer polymer and the epoxy resin can generate a crosslinking reaction, and the function of a molecular bridge is achieved; the adhesive also can play a role of a tackifier, effectively improves the bonding strength of the adhesive, and also improves the water resistance and the weather resistance; (4) the flexible copper-clad plate prepared by the adhesive has low dielectric loss, high weather resistance and high bending resistance, meets the special requirements on the flexible copper-clad plate under the development of a high-frequency novel information product, and ensures that the flexible copper-clad plate can maintain good product stability and service life in various extreme environments and applications; (5) the stepwise curing treatment in the preparation process of the soft copper-clad plate can promote the gradual movement of molecular chains by gradually increasing the temperature, is beneficial to the curing reaction of the epoxy resin in the component A and the component B, enables the curing reaction of the product to be balanced and cured completely, and effectively ensures the stability of the finished product of the soft copper-clad plate.
Drawings
FIG. 1 is a schematic structural diagram of the flexible copper clad laminate of the present invention.
Wherein: a substrate layer 1; an adhesive layer 2; a copper foil layer 3.
Detailed Description
The technical solutions of the present invention will be described in detail below in order to clearly understand the technical features, objects, and advantages of the present invention, but the present invention is not limited to the practical scope of the present invention.
The invention provides an adhesive which is formed by mixing a component A and a component B, wherein the component A comprises the following raw materials in parts by mass: 50-60 parts of fluorine-containing elastomer polymer, 20-40 parts of epoxy resin, 40-80 parts of organic solvent, 5-10 parts of environment-friendly flame-retardant filler, 1.5-5 parts of impact modifier, 0.5-1 part of silane coupling agent and 0.1-1 part of reaction promoter;
the component B comprises the following raw materials in parts by mass: 2-4 parts of a curing agent and 2-10 parts of an organic solvent;
the solid content ratio of the component A and the component B when mixed is 10: (0.2-0.4).
The adhesive is used for the flexible copper-clad plate, and the fluorine-containing elastomer polymer, the epoxy resin and the silane coupling agent are ingeniously compounded for use, so that the high adhesion performance of the adhesive to be bonded is obviously improved, the dielectric constant of a bonded product is reduced, the dielectric loss is reduced, the weather resistance and the bending resistance of the bonded product are improved, the special requirements of the development of high-frequency novel information products are met, and the bonded product can keep good product stability and service life in various extreme environments and applications.
The core component in the formula of the first component of the adhesive is a fluorine-containing elastomer polymer, so that the adhesive has good low dielectric property, medium resistance and non-flammability, and the dielectric loss is effectively reduced; the fluorine-containing elastomer polymer has excellent stability, and perfect lamination is realized through the adhesive bonding material, so that the bonded product has higher weather resistance; the fluorine-containing elastomer polymer has good elasticity and recoverability, and endows the bonded product with strong bending resistance and good deformation recovery capability; but the fluorine-containing elastomer polymer has poor metal bonding force, and can effectively improve and enhance the adhesive force performance of the adhesive to metal materials by being mixed with epoxy resin, thereby meeting the requirements of flexible copper clad laminate products.
The epoxy resin plays a role of a carrier in the adhesive, has good dielectricity, high and low temperature resistance, water absorption resistance and the like, can improve the stability and weather resistance of the required adhesive, has good impact toughness and bonding property, and can improve the adhesive force and impact property of the epoxy resin to the surface of a metal material when being mixed with the fluorine-containing elastomer polymer. However, the epoxy resin has a certain brittleness, and the addition amount of the epoxy resin is not suitable to be high in order to keep high elasticity and improve the durability of a bonded product; moreover, the epoxy resin has a high dielectric constant, which is not favorable for reducing the dielectric loss of the bonded product, so the proportion of the added amount is not too large and is lower than that of the fluorine-containing elastomer polymer, thereby ensuring that the low dielectric property of the fluorine-containing elastomer polymer can be exerted.
The silane coupling agent can react with the environment-friendly flame-retardant filler, so that the applicability and the dispersibility of the environment-friendly flame-retardant filler are improved; the fluorine-containing elastomer polymer and the epoxy resin can generate a crosslinking reaction, and the function of a molecular bridge is achieved; the adhesive can also play a role of a tackifier, effectively improves the bonding strength of the adhesive, and also improves the water resistance and the weather resistance. However, the excessive addition of the silane coupling agent can cause the excessive viscosity of the adhesive to influence the processing performance, and the viscosity and the crosslinking effect of the adhesive are effectively ensured according to the formula amount.
The environment-friendly flame-retardant filler can effectively control the water absorption resistance and viscosity of the adhesive, but excessive addition of the filler can increase the viscosity of the adhesive and prolong the processing time, so the filler is preferably added according to the formula amount.
The impact modifier can adjust the brittleness of the adhesive after bonding, can effectively control the brittleness of the adhesive after bonding by controlling the addition within the range of formula amount, and simultaneously controls the cost.
The reaction accelerator can react with the curing agent, can effectively accelerate the curing of the binder, and reduce the reaction temperature, so that the adhesive layer can reach a stable curing state in a thermal curing stage more quickly.
The organic solvent is used for dissolving substances which are difficult to dissolve in water, and the solid content of the adhesive is adjusted to reach proper solid content, so that the texture of the adhesive is adjusted.
In conclusion, the adhesion capability of the fluorine-containing elastomer polymer to the base material is poor, the adhesion performance of the adhesive to the material to be adhered is influenced to a certain extent, but after the silane coupling agent is added into the mixture of the fluorine-containing elastomer polymer and the epoxy resin for crosslinking, the modification effect is achieved, and the adhesion force of the fluorine-containing elastomer polymer to the base material is greatly improved. Meanwhile, the addition of the silane coupling agent can enable the fluorine-containing elastomer polymer and the epoxy resin to perform a crosslinking reaction and support a molecular bridge, so that the fluorine-containing elastomer polymer and the epoxy resin are mixed more stably, and the adhesive has stronger and more durable adhesive property. Therefore, the fluorine-containing elastomer polymer, the epoxy resin and the silane coupling agent are compounded for use, so that the main agent of the component A of the adhesive is formed, the adhesion performance of the fluorine-containing elastomer polymer to a base material and the outer surface of metal is effectively improved, the adhesive has high adhesion performance to a material to be bonded, the combination energy among the components is more stable, the abnormity of component compatibility is avoided, and meanwhile, the low dielectric property, high weather resistance and high bending resistance of the fluorine-containing elastomer polymer are exerted. On the basis, the component A is formed by adding the environment-friendly flame-retardant filler, the impact modifier, the reaction promoter and the organic solvent, so that the water absorption resistance, the viscosity, the brittleness and the solid content of the component A are further adjusted. And finally, the adhesive is mixed with a component B containing a curing agent, so that the stability of the adhesive is improved, the curing performance of the adhesive is optimized, the obvious high adhesive force of the adhesive to materials to be bonded is exerted, the bonded product is promoted to have the capabilities of low dielectric property, weather resistance and bending resistance, the stability is improved, and the service life is prolonged. The problems of high dielectric loss, unstable performance and short service life of products prepared by using the conventional adhesive due to the high dielectric constant, poor weather resistance and poor bending resistance are solved.
Further, the fluorine-containing elastomer polymer is one or more of epoxy resin modified vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer, chlorotrifluoroethylene-vinylidene fluoride copolymer, polytetrafluoroethylene modified styrene-butadiene/nitrile rubber, vinylidene fluoride-tetrafluoroethylene-perfluoromethyl vinyl ether-vulcanization point monomer quadripolymer and tetrafluoroethylene-hydrocarbon propylene copolymer;
the epoxy resin is one or more of polyphenol type glycidyl ether epoxy resin, heterocyclic type glycidyl epoxy resin, organic titanium modified bisphenol A type epoxy resin, glycidyl amine type epoxy resin and aliphatic epoxidized olefin compound;
the environment-friendly flame-retardant filler is prepared from a phosphorus flame retardant and an inorganic salt flame retardant in a weight ratio of 1: (1-3), wherein the phosphorus flame retardant is one or more of ammonium polyphosphate, hypophosphite, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, triphenyl phosphorus oxide, diethyl aluminum hypophosphite and resorcinol bis (2, 6-dimethylphenyl) phosphate; the inorganic salt flame retardant is one or more of aluminum hydroxide, magnesium hydroxide, zinc borate and silicate;
the impact modifier is one or more of chlorinated polyvinyl chloride, ethylene-vinyl acetate copolymer and 4, 5-epoxy tetrahydrophthalic dioctyl ester;
the silane coupling agent is one or more of gamma-glycidyl ether propyl trimethoxy silane, 3-glycidyl ether oxygen propyl triethoxy silane, 3-glycidyl ether oxygen propyl trimethoxy silane and 2- (3, 4-epoxy cyclohexyl) ethyl trimethoxy silane;
the reaction accelerator is one or more of organic urea, N' -diphenylguanidine, N-diethylaniline and 2,4, 6-tris (dimethylaminomethyl) phenol;
the curing agent is one or more of amino resin crosslinking polycondensation-acrylate polymerization system curing agent, dicyandiamide latent curing agent and mixed polyisocyanate curing agent;
the organic solvent is one or more of butanone, acetone, cyclohexane, cyclohexanone, toluene, xylene and N, N-dimethylformamide.
The fluorine-containing elastomer polymer has good low dielectric property, medium resistance and non-flammability, excellent thermoplastic fluidity and thermal stability and higher weather resistance. Meanwhile, the fluorine-containing elastomer polymer has good elasticity and recoverability, and endows the bonded product with strong bending resistance and good deformation recovery capability.
The epoxy resin has good dielectricity, high and low temperature resistance, water absorption resistance and the like, can improve the stability and weather resistance of the required adhesive, has good impact toughness and bonding property, and can improve the adhesive force and impact property of the epoxy resin on the surface of a metal material when being mixed with the fluorine-containing elastomer polymer.
The flame retardant property of the bonded product is effectively improved by adding the environment-friendly flame retardant filler, and the halogen-free and ROSH-free products meet the environment-friendly requirement. But when the phosphorus flame retardant is used alone, the flame retardant effect is poor, and the phosphorus flame retardant and the inorganic salt flame retardant can generate a synergistic effect after being compounded, so that the flame retardant efficiency and the smoke suppression effect are improved, the dispersity is improved, the compatibility with a polymer is improved, and the impact resistance and the thermal property are improved, so that the good flame retardant effect is obtained.
The impact modifier can improve the storage stability of the adhesive, and simultaneously has the functions of toughening, low-temperature stability, durability and mechanical property modification. The silane coupling agent plays a role of a tackifier, effectively improves the bonding strength of the adhesive, and can also improve the performances of water resistance, weather resistance and the like. The reaction promoter can react with the curing agent, can effectively accelerate the curing of the adhesive and reduce the reaction temperature. The curing agent can effectively improve the stability of the adhesive, reduce the curing temperature, improve the curing rate and better improve the adhesion, thermal stability and weather resistance of the bonding layer. The organic solvent is used for dissolving substances which are difficult to dissolve in water, and the solid content of the adhesive is adjusted to reach proper solid content, so that the texture of the adhesive is adjusted.
The preparation method of the adhesive comprises the following steps:
(a) mixing a fluorine-containing elastomer polymer, epoxy resin and an organic solvent of the component A according to a formula amount, stirring at a constant temperature, adding a silane coupling agent according to the formula amount, and stirring at a reduced speed for 40-60 min to obtain a main agent of the component A;
(b) preparing an environment-friendly flame-retardant filler, adding an impact modifier and the environment-friendly flame-retardant filler into a component A main agent according to the formula amount, stirring for 60-90 min at the rotating speed of 1000-3000 rpm, adding a reaction promoter according to the formula amount after uniformly stirring, and stirring for 10-15 min at the rotating speed of 1000-3000 rpm to obtain a component A;
(c) mixing and dissolving a curing agent and an organic solvent of the component B according to the formula amount to obtain the component B;
(d) and mixing the component A and the component B according to a proportion, stirring for 30-40 min, and sieving to obtain the adhesive.
The fluorine-containing elastomer polymer and the epoxy resin are dissolved in the organic solvent and the solid content is regulated, and the constant-temperature stirring treatment is carried out, so that the main components of the component A are uniformly mixed and fully reacted at the set temperature and the set rotating speed, a stable molten state is achieved, and the stability of the main agent of the component A is improved. The high-speed stirring in the early stage is to ensure that the fluorine-containing elastomer polymer and the epoxy resin are fully and uniformly stirred, and the subsequent speed reduction stirring is to add the silane coupling agent to ensure the stable progress of the crosslinking reaction after the silane coupling agent is added. When the impact modifier and the environment-friendly flame-retardant filler are added into the main agent of the component A according to the formula amount, the viscosity of the component A can be obviously increased by the environment-friendly flame-retardant filler, so that the stirring resistance is increased, the stirring rotating speed is obviously improved, the mixing and reaction among raw materials are facilitated, and the preparation efficiency and the quality of the component A are improved. The organic solvent is utilized to dissolve the curing agent in advance to prepare a solution, and then the solution is mixed and stirred with the component A, so that the reaction efficiency between the component A and the component B is improved, and the prepared adhesive can achieve the expected effect. In the whole preparation process, the organic solvent adjusts the solid content of the adhesive to be 25-60%. And mixing the component A and the component B in proportion, stirring, fully mixing uniformly, sieving, and separating out larger particles in the adhesive, so that the fineness and viscosity of the prepared adhesive meet the requirements, and the performance of the prepared adhesive is ensured to reach the standard.
Further, in the step (a), the parameters of the constant-temperature stirring treatment are as follows: the temperature is one of 60 ℃ to 80 ℃, the rotating speed is 1000rpm to 1500rpm, the time is 4 hours, the temperature of constant-temperature stirring treatment is kept in the process of adding the silane coupling agent, and the rotating speed of speed reduction stirring is 500rpm to 800 rpm.
And (b) stirring at constant temperature in the step (a) to promote the full mixing of the fluorine-containing elastomer polymer and the epoxy resin, wherein the heating temperature is 60-80 ℃, and the temperature is also kept in the adding process of the silane coupling agent to keep the reactivity of the silane coupling agent. The former high speed is to fully and uniformly stir the fluorine-containing elastomer polymer and the epoxy resin, and the latter speed reduction is to add the silane coupling agent to ensure the stable progress of the crosslinking reaction after the coupling agent is added.
Further, the stirring speed of the step (d) is 800-1500 rpm, and the number of the sieving meshes is 300-400 meshes. The stirring speed in the step (d) is high-speed, the mixing speed of the component A and the component B is obviously increased, the preparation efficiency of the adhesive is improved, the mixing effect of the component A and the component B is improved, and the performance stability of the adhesive is improved. And mixing and stirring the component A and the component B according to a ratio, sieving the mixture by a 300-400-mesh sieve, and separating out larger particles in the adhesive to ensure that the fineness of the prepared adhesive is less than or equal to 10 mu m and the viscosity of the prepared adhesive is 2000-3500 mPa.s, so as to ensure that the performance of the prepared adhesive reaches the standard.
The utility model provides an use soft copper-clad plate of above-mentioned gluing agent, as shown in figure 1, includes substrate layer 1, adhesive linkage 2 and copper foil layer 3, and adhesive linkage 2 is formed by gluing agent coating, and adhesive linkage 2 bonds substrate layer 1 and copper foil layer 3 together.
According to the invention, the adhesive layer 2 is formed by coating the adhesive, so that the high adhesion performance of the adhesive to the substrate layer 1 and the copper foil layer 3 is obviously improved, the low dielectric loss of the flexible copper-clad plate is reduced, and the weather resistance and the bending resistance of the flexible copper-clad plate are improved, so that the special requirements of the development of a novel high-frequency information product on the flexible copper-clad plate are met, and the flexible copper-clad plate can maintain good product stability and service life in various extreme environments and applications.
The performance-improving structure of the soft copper-clad plate is an adhesive layer 2 formed by coating an adhesive, the core component in the adhesive A component formula is a fluorine-containing elastomer polymer, and the fluorine-containing elastomer polymer has good low dielectric property, medium resistance and non-combustibility, so that the dielectric loss of the soft copper-clad plate is effectively reduced; the fluorine-containing elastomer polymer has excellent stability, and the base material layer 1 and the copper foil layer 3 bonded by the adhesive are perfectly attached, so that the flexible copper clad laminate has higher weather resistance; the fluorine-containing elastomer polymer has good elasticity and recoverability, and endows the flexible copper-clad plate with strong bending resistance and good deformation recovery capability; however, the fluorine-containing elastomer polymer itself has poor adhesion to metal, and when it is used in combination with an epoxy resin, the adhesion to copper foil layer 3 can be effectively improved.
The fluorine-containing elastomer polymer is poor in adhesion capability to the base material layer 1, the adhesion performance of the adhesive to the base material layer 1 can be affected to a certain extent, but after the silane coupling agent is added into a mixture of the fluorine-containing elastomer polymer and epoxy resin for crosslinking, a modification effect is achieved, and the adhesion force of the fluorine-containing elastomer polymer to the base material is greatly improved. Meanwhile, the addition of the silane coupling agent can enable the fluorine-containing elastomer polymer and the epoxy resin to perform a crosslinking reaction and support a molecular bridge, so that the fluorine-containing elastomer polymer and the epoxy resin are mixed more stably, and the adhesive has stronger and more durable adhesive property. Therefore, the fluorine-containing elastomer polymer, the epoxy resin and the silane coupling agent are compounded for use, so that the main agent of the component A of the adhesive is formed, the adhesion performance of the fluorine-containing elastomer polymer to the outer surfaces of the base material and the metal is effectively improved, the adhesive has high adhesion performance to the base material layer 1 and the copper foil layer 3, the combination performance among the components is more stable, the abnormity of component compatibility is avoided, and meanwhile, the low dielectric property, high weather resistance and high bending resistance of the fluorine-containing elastomer polymer are exerted. On the basis, the component A is formed by adding the environment-friendly flame-retardant filler, the impact modifier, the reaction promoter and the organic solvent, so that the water absorption resistance, the viscosity, the brittleness and the solid content of the component A are further adjusted. And finally, the adhesive is mixed with a component B containing a curing agent, so that the stability of the adhesive is improved, the curing performance of the adhesive is optimized, and the high adhesive force of the adhesive on the substrate layer 1 and the copper foil layer 3 is exerted, so that the soft copper-clad plate has the capabilities of low dielectric property, weather resistance and bending resistance, the stability is improved, and the service life is prolonged. Solves the problems of high dielectric loss, unstable performance and short service life of the existing soft copper-clad plate due to the poor high dielectric constant, weather resistance and bending resistance.
Further, the substrate layer 1 is a biaxially oriented substrate film, and the substrate film is one of a PI film, a PEFT film, a PEN film, and an Aramid film; the copper foil layer 3 is electrolytic copper foil or rolled copper foil;
the thickness of the substrate layer 1 is 15-110 μm; the thickness of the bonding layer 2 is 5-70 μm; the thickness of the copper foil layer 3 is 12 to 150 μm.
The base material film is one of a PI (polyimide) film, a PEFT (polytetrafluoroethylene) film, a PEN (polyethylene naphthalate) film and an Aramid (asymmetric aromatic polyamide) film, and is made of an insulating film material, so that the flexible copper-clad plate is protected from being invaded by external substances while the insulating function of the base material film is exerted, the flexible copper-clad plate is more durable, and the performance of the flexible copper-clad plate is more stable; the copper foil layer 3 provides a conductor material, and is a material for realizing the function of a conductor by a soft copper-clad plate.
And adjusting the thickness of each layer of the flexible copper-clad plate according to the actual use requirement. The key point of the invention is that the bonding layer 2 has a thickness of 5-70 μm, thus realizing low dielectric property, high weather resistance and high bending resistance of the whole soft copper-clad plate, having obvious effect and thinner thickness, effectively reducing the thickness of the soft copper-clad plate and saving cost.
A preparation method of the flexible copper-clad plate using the adhesive comprises the following steps:
(1) carrying out corona treatment on the surface of the substrate layer 1;
(2) carrying out chemical cleaning and mechanical grinding treatment on the surface of the copper foil layer 3 to enable the surface of the copper foil layer 3 to have a rough surface, and obtaining a pretreated copper foil layer 3;
(3) coating an adhesive on the corona treatment surface of the substrate layer 1 to enable the substrate layer 1 to be provided with the bonding layer 2, and drying to obtain a bonding substrate layer 1;
(4) bonding the bonding surface of the bonding substrate layer 1 with the rough surface of the pretreated copper foil layer 3, performing normal-temperature roller pre-lamination, and then performing high-temperature hot roller lamination, wherein the temperature of the high-temperature hot roller lamination is set to be 110-150 ℃, so as to obtain a semi-finished product of the flexible copper-clad plate;
(5) and (4) after the soft copper-clad plate semi-finished product is unwound, performing staged curing treatment to obtain a soft copper-clad plate finished product.
Corona treatment is carried out on the surface of the base material layer 1, the surface of the base material layer 1 is improved, higher adhesiveness is achieved, and various abnormal problems caused by insufficient adhesive force between the adhesive layer 2 and the base material layer 1 are avoided. And carrying out chemical cleaning and mechanical grinding treatment on the surface of the copper foil layer 3 to ensure that the surface of the copper foil layer 3 has a rough surface and improve the adhesive force of the adhesive layer 2 to the copper foil layer 3. And coating an adhesive on the corona treatment surface of the substrate layer 1, and then drying, effectively drying the solvent, and removing the residual organic solvent after the adhesive is prepared. After the bonding surface of the bonding substrate layer 1 is bonded with the rough surface of the pretreated copper foil layer 3, pre-laminating the substrate layer 1, the bonding layer 2 and the copper foil layer 3 by a normal-temperature roller so as to improve the smooth bonding degree of the substrate layer 1, the bonding layer 2 and the copper foil layer 3 in the rolling process; and (3) laminating by using a high-temperature hot roller, and rolling by using the high temperature of 110-150 ℃, so that the laminating effect among the substrate layer 1, the bonding layer 2 and the copper foil layer 3 can be obviously improved, and the adhesion effect of the bonding layer 2 to the substrate layer 1 and the copper foil layer 3 respectively is improved. And finally, the stepwise curing treatment can promote the gradual movement of the molecular chain, is beneficial to the curing reaction of the epoxy resin in the component A and the component B, ensures the curing reaction of the product to be balanced and the curing to be complete, and effectively ensures the stability of the finished product of the flexible copper-clad plate.
Further, the corona value set in the corona treatment of the step (1) is greater than 52 dy; the speed of coating the adhesive in the step (3) is 2-10 m/min, and the temperature of drying treatment is 140-220 ℃.
The corona value set in the corona treatment is greater than 52dy, so that the surface of the base material layer 1 is effectively ensured to have higher adhesiveness, and various abnormal problems caused by insufficient adhesive force between the adhesive layer 2 and the base material layer 1 are avoided. And high-temperature drying treatment is carried out, so that the residual organic solvent after the preparation of the adhesive is finished is efficiently removed, the production efficiency of the flexible copper-clad plate is improved, and the stability of the adhesive is improved. The set speed of coating the adhesive is related to the organic solvent used in the preparation process of the adhesive, and meanwhile, the set temperature and the used drying equipment in the subsequent drying treatment are also referred to, so that the speed of coating the adhesive is set within a proper range, and the organic solvent can be effectively dried as much as possible in the subsequent drying treatment process.
Further, the step-type curing treatment in the step (5): the temperature is increased from 30 ℃ to 100 ℃ in 100min in the first stage; the second stage is to keep the temperature at 100 ℃ within 120 min; in the third stage, the temperature is increased from 100 ℃ to 150 ℃ within 180 min; the fourth stage is to maintain the temperature at 150 ℃ within 120 min; in the fifth stage, the temperature is increased from 150 ℃ to 180 ℃ within 120 min; the temperature dropped from 180 ℃ to 30 ℃ in the sixth stage within 60 min.
The staged curing treatment is adopted because the adhesive is a multi-component mixture, if one-time heating is adopted, the curing reaction is too violent, so that by-products are generated, the internal and external curing of the adhesive is not uniform, and the adverse problems of large stress, reduced performance and the like of a product are caused; in addition, if mixed organic solvents are adopted in the preparation of the adhesive, wherein the boiling points of different solvents are different, the residual solvent can be effectively volatilized by adopting the stepwise gradual heating and curing, and the influence of the residual organic solvent is further avoided. The gradual temperature rise in the stage curing process can promote the gradual movement of molecular chains, is beneficial to the curing reaction of the epoxy resin in the component A and the component B, enables the curing reaction of the product to be balanced and the curing to be complete, and effectively ensures the stability of the finished product of the soft copper-clad plate.
Example group A
1. Preparation of adhesive
(a) Mixing polytetrafluoroethylene modified styrene-butadiene/nitrile rubber, polyphenol type glycidyl ether epoxy resin and cyclohexane according to a formula amount set in the following table I, stirring at a constant temperature of 1500rpm and 80 ℃ for 4 hours, then adding gamma-glycidyl ether propyl trimethoxy silane according to the formula amount under the condition of keeping the constant temperature, reducing the speed to 800rpm, and stirring for 60 minutes to obtain a component A main agent;
(b) mixing ammonium polyphosphate and aluminum hydroxide in a mass ratio of 1:1 to prepare an environment-friendly flame-retardant filler; adding chlorinated polyvinyl chloride and an environment-friendly flame-retardant filler into a main agent of the component A according to the formula amount set in the following table I, stirring for 90min at the rotating speed of 3000rpm, adding N, N' -diphenyl guanidine according to the formula amount after uniformly stirring, and stirring for 15min at the rotating speed of 3000rpm to obtain the component A;
(c) mixing and dissolving dicyandiamide latent curing agent, N' -diphenyl guanidine and acetone according to the formula amount set in the following table I to prepare a component B;
(d) mixing the component A and the component B according to the proportion of 10: mixing the components according to the solid content ratio of 0.2, stirring for 40min at the rotating speed of 1500rpm, and sieving by a 400-mesh sieve to obtain the adhesive.
2. Preparation of flexible copper-clad plate
(1) Carrying out corona treatment on the surface of the substrate layer 1, wherein the corona value is set to be 55dy, and the thickness of the substrate layer 1 is 15 microns;
(2) carrying out chemical cleaning and mechanical grinding treatment on the surface of the copper foil layer 3, wherein the thickness of the copper foil layer 3 is 12 microns, so that the surface of the copper foil layer 3 is provided with a rough surface, and obtaining a pretreated copper foil layer 3;
(3) coating an adhesive on the corona treatment surface of the substrate layer 1 at a speed of 10m/min, wherein the thickness of the bonding layer 2 is 20 microns, so that the substrate layer 1 is provided with the bonding layer 2, and drying at 220 ℃ to obtain the bonding substrate layer 1;
(4) bonding the bonding surface of the bonding substrate layer 1 with the rough surface of the pretreated copper foil layer 3, performing normal-temperature roller pre-lamination, and then performing high-temperature hot roller lamination, wherein the temperature of the high-temperature hot roller lamination is set to be 150 ℃, so as to obtain a semi-finished product of the flexible copper-clad plate;
(5) after the soft copper-clad plate semi-finished product is unwound, performing staged curing treatment: the temperature is increased from 30 ℃ to 100 ℃ in 100min in the first stage; the second stage is to keep the temperature at 100 ℃ within 120 min; in the third stage, the temperature is increased from 100 ℃ to 150 ℃ within 180 min; the fourth stage is to maintain the temperature at 150 ℃ within 120 min; in the fifth stage, the temperature is increased from 150 ℃ to 180 ℃ within 120 min; in the sixth stage, the temperature is reduced from 180 ℃ to 30 ℃ within 60min, and the finished product of the flexible copper-clad plate is obtained.
Table one example group a adhesive ingredient content setting table
Figure BDA0001876476960000171
The examples A1-A5 were prepared according to the above method and were tested for performance, the results of which are shown in Table II below:
TABLE II EXAMPLES group A Performance test
Figure BDA0001876476960000172
Figure BDA0001876476960000181
As can be seen from Table II, the appearance of the flexible copper clad laminate prepared in the embodiment A1-A5 is very little or has no defects such as discoloration, concave-convex, crease, wrinkle, bubble, shrinkage cavity and the like, and the performance test of the flexible copper clad laminate prepared in the embodiment A1-A5 shows that the dielectric constant is less than or equal to 2.85 and the dielectric loss is less than or equal to 0.00 at the frequency of 10GHz1, surface insulation resistance is not less than 1.0 x 1014Omega, the peel strength is within the range of 1.45-1.52N/mm, the overall flame retardant property reaches UL94VTM-0 grade, and the soldering resistance is good without abnormity. The combination of the high-temperature high-humidity test, the high-low-temperature impact test, the high-low-temperature peeling test and the circulating temperature test verifies that the weather resistance of the sample is extremely stable, the change is little and the abnormality is little, which shows that the soft copper-clad plate prepared in the embodiment A1-A5 has extremely high weather resistance and extremely high stability under various extreme environmental factors; and also has high bending resistance which can reach more than 1000000 times, and also has extremely high bending resistance service life. Therefore, the flexible copper clad laminate prepared in the embodiment A1-A5 can have low dielectric loss, and improve the weather resistance and the bending resistance.
Example group B
1. Preparation of adhesive
(a) Mixing 50g of fluorine-containing elastomer polymer, 20g of epoxy resin and 40g of organic solvent, stirring at the constant temperature of 1000rpm and 60 ℃ for 4h, then adding the silane coupling agent with the formula amount under the condition of keeping the constant temperature, reducing the speed to 500rpm, and stirring for 40min to obtain a component A main agent; specific components of the fluorine elastomer polymer, the epoxy resin, the organic solvent and the silane coupling agent are arranged according to the third table;
(b) mixing a phosphorus flame retardant and an inorganic salt flame retardant in a mass ratio of 1:3 to prepare an environment-friendly flame-retardant filler; adding 1.5g of impact modifier and 5g of environment-friendly flame-retardant filler into the main agent of the component A, stirring for 60min at the rotating speed of 1000rpm, adding 0.1g of reaction accelerator after stirring uniformly, and stirring for 10min at the rotating speed of 1000rpm to obtain the component A; the specific components of the phosphorus flame retardant, the inorganic salt flame retardant, the impact modifier and the reaction accelerator are arranged according to the third table;
(c) mixing and dissolving 2g of curing agent and 2g of organic solvent to prepare a component B; the concrete components of the curing agent and the organic solvent are arranged according to the third table;
(d) mixing the component A and the component B according to the proportion of 10: mixing the components according to the solid content ratio of 0.4, stirring the mixture for 30min at the rotating speed of 800rpm, and sieving the mixture by a 300-mesh sieve to obtain the adhesive.
2. Preparation of flexible copper-clad plate
(1) Carrying out corona treatment on the surface of the substrate layer 1, and setting the thickness and the corona value of the substrate layer 1 according to a fourth table;
(2) carrying out chemical cleaning and mechanical grinding treatment on the surface of the copper foil layer 3 to enable the surface of the copper foil layer 3 to have a rough surface, and obtaining a pretreated copper foil layer 3;
(3) coating an adhesive on the corona treatment surface of the substrate layer 1 at the speed of 2m/min to enable the substrate layer 1 to be provided with an adhesive layer 2, setting the thickness of the adhesive layer 2 according to the fourth table, and drying at 140 ℃ to obtain the adhesive substrate layer 1;
(4) bonding the bonding surface of the bonding substrate layer 1 with the rough surface of the pretreated copper foil layer 3, setting the thickness of the copper foil layer 3 according to the fourth table, carrying out normal-temperature roller pre-lamination, and then carrying out high-temperature hot roller lamination, wherein the temperature of the high-temperature hot roller lamination is set to be 110 ℃, so as to obtain a semi-finished product of the flexible copper-clad plate;
(5) after the soft copper-clad plate semi-finished product is unwound, performing staged curing treatment: the temperature is increased from 30 ℃ to 100 ℃ in 100min in the first stage; the second stage is to keep the temperature at 100 ℃ within 120 min; in the third stage, the temperature is increased from 100 ℃ to 150 ℃ within 180 min; the fourth stage is to maintain the temperature at 150 ℃ within 120 min; in the fifth stage, the temperature is increased from 150 ℃ to 180 ℃ within 120 min; in the sixth stage, the temperature is reduced from 180 ℃ to 30 ℃ within 60min, and the finished product of the flexible copper-clad plate is obtained.
TABLE TRI EXAMPLES group B specific composition settings
Figure BDA0001876476960000201
Figure BDA0001876476960000211
TABLE IV EXAMPLES Table for corona values and layer thickness settings
Figure BDA0001876476960000212
The examples B1-B5 were prepared according to the above method and were tested for their performance as shown in the following Table V:
table five examples group B performance testing
Figure BDA0001876476960000213
Figure BDA0001876476960000221
As can be seen from the table five, the appearance of the finished soft copper-clad plate prepared in the embodiment B1-B4 is very little or has no defects such as color change, concave-convex, crease, wrinkle, bubble, shrinkage cavity and the like, and the performance test of the finished soft copper-clad plate prepared in the embodiment B1-B4 shows that the dielectric constant is less than or equal to 2.87, the dielectric loss is less than or equal to 0.0012 and the surface insulation resistance is more than or equal to 1.0 multiplied by 10 at the frequency of 10GHz14Omega, the peel strength is within the range of 1.39-1.56N/mm, the overall flame retardant property reaches UL94VTM-0 grade, and the soldering resistance is good without abnormity. The combination of the high-temperature high-humidity test, the high-low-temperature impact test, the high-low-temperature peeling test and the circulating temperature test verifies that the weather resistance of the sample is extremely stable, the change is little and the abnormality is little, which shows that the finished product of the soft copper-clad plate prepared in the embodiment B1-B4 has extremely high weather resistance and extremely high stability under various extreme environmental factors; and also has high bending resistance which can reach more than 1000000 times, and also has extremely high bending resistance service life. Therefore, the finished soft copper clad laminate prepared in the embodiment B1-B4 has low dielectric loss, high weather resistance and high bending resistance compared with the existing soft copper clad laminate.
As can be seen from table five, the finished flexible copper clad laminate prepared in example B5 does not pass the-65 ℃ high and low temperature impact test, does not pass the-65 ℃ to 160 ℃ circulating temperature test, does not pass the 200000 times flexing endurance test and 1000000 times flexing endurance test, and thus when the corona value is set to 52dy, the flexing endurance of the finished flexible copper clad laminate is affected, the adhesion of the surface of the substrate layer 1 is affected, and the product quality is reduced.
The specific method for testing the performance of the finished product of the flexible copper-clad plate prepared by the embodiment comprises the following steps:
(1) appearance: visual observation is carried out to determine whether the surface of the finished product of the flexible copper-clad plate has defects such as color change, concave-convex, crease, wrinkle, bubble, shrinkage cavity and the like.
(2) Dielectric constant and dielectric loss: the high-frequency dielectric property of the finished product of the flexible copper-clad plate can be verified by adopting a separated dielectric resonant cavity method for testing, wherein the testing frequency is 10 GHZ.
(3) Surface insulation resistance: and (3) preparing a test sample of the finished soft copper-clad plate by adopting an instrument specified in JISC1303 according to the standard, applying DC 500V voltage on the finished soft copper-clad plate to be tested, keeping the voltage for 1min, and measuring the surface insulation resistance under the applied voltage.
(4) Peel strength: and (4) cutting the finished product of the soft copper-clad plate into a spline with the thickness of 3.0 +/-1 mm multiplied by 100mm according to IPC-TM650-2.4.9D, and testing the 90-degree peeling force at the speed of 50mm/min by adopting a peeling force testing machine to verify the bonding force of the bonding layer 2 of the finished product of the soft copper-clad plate to be tested.
(5) Solder resistance test: cutting the finished product of the flexible copper-clad plate into a sample with the size of 30mm multiplied by 30mm, respectively setting the temperature of 288 ℃ and 300 ℃ by adopting a soldering tin furnace, immersing the sample into the soldering tin furnace for 30 seconds of tin immersion test, and observing whether the abnormality such as air bubbles, delamination, discoloration, separation and the like exists.
(6) Flame retardant property: and testing by adopting a UL94VTM testing method to verify the flame retardant grade of the finished product of the flexible copper-clad plate.
(7) And (3) weather resistance test: the test is comprehensively verified by a high-temperature high-humidity test, a high-low temperature impact test, a high-low temperature peeling test, a circulating temperature test and the like. The specifications of the prepared test samples are as follows: 15. + -. 1mm X130. + -.5 mm.
High temperature and high humidity test: the temperature is 85 +/-5 ℃ and the humidity is 85 +/-5%, the finished product of the soft copper-clad plate is placed in a constant temperature and humidity box for 96 hours, the problems of oxidation, foaming, stripping and layering abnormality on the surface of a tested sample are observed, the stripping force is tested, and the change rate is less than or equal to 10%.
High and low temperature impact test: and measuring to obtain the surface resistance of the sample, placing the test sample in a high-low temperature testing machine, setting the temperature to be-65 ℃, 20 ℃, 100 ℃ and 160 ℃, respectively placing for 30min, observing whether the surface of the tested sample has the problems of oxidation, foaming, stripping and layering abnormity, and ensuring that the surface resistance change rate before and after the test is less than or equal to 10%.
High and low temperature peel force test: placing the sample in a high-low temperature tensile machine, respectively setting the temperature at-50 ℃,10 ℃, 100 ℃ and 150 ℃, and testing and recording the stripping of the sample at corresponding temperature.
And (3) testing the circulating temperature: the sample is placed in a precision convection high-low temperature oven, the program is set to have low-high temperature circulation, the low temperature is set to be-65 ℃, the high temperature is set to be 160 ℃, the high-low temperature constant temperature time is 15min, the temperature conversion time is 10min, and the circulation is continued for 5 times. And observing whether the tested sample has the problems of oxidation, foaming, stripping and delamination after the test.
(8) And (3) bending resistance test: with reference to the standard IPC-TM650, test specimens with the specification of 15 +/-1 mm multiplied by 130 +/-5 mm are prepared, a 4.9N (0.5kgf) load is set, the bending radius is 2mm, the bending angle is 135 +/-5 degrees, the test is carried out at the speed of about 170 times/min, and whether the sample has the abnormalities such as cracking, whitening, degumming and the like at each stage is observed.
The technical principle of the present invention is described above in connection with specific embodiments. The description is made for the purpose of illustrating the principles of the invention and should not be construed in any way as limiting the scope of the invention. Based on the explanations herein, those skilled in the art will be able to conceive of other embodiments of the present invention without inventive effort, which would fall within the scope of the present invention.

Claims (10)

1. An adhesive, characterized in that: the adhesive is formed by mixing a component A and a component B, wherein the component A comprises the following raw materials in parts by mass: 50-60 parts of fluorine-containing elastomer polymer, 20-40 parts of epoxy resin, 40-80 parts of organic solvent, 5-10 parts of environment-friendly flame-retardant filler, 1.5-5 parts of impact modifier, 0.5-1 part of silane coupling agent and 0.1-1 part of reaction promoter; the fluorine-containing elastomer polymer is one or more of epoxy resin modified vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer, chlorotrifluoroethylene-vinylidene fluoride copolymer, polytetrafluoroethylene modified styrene-butadiene/nitrile rubber, vinylidene fluoride-tetrafluoroethylene-perfluoromethyl vinyl ether-vulcanization point monomer quadripolymer and tetrafluoroethylene-hydrocarbon propylene copolymer;
the component B comprises the following raw materials in parts by mass: 2-4 parts of a curing agent and 2-10 parts of an organic solvent;
the solid content ratio of the component A to the component B when mixed is 10: (0.2-0.4).
2. The adhesive of claim 1, wherein: the epoxy resin is one or more of polyphenol type glycidyl ether epoxy resin, heterocyclic type glycidyl epoxy resin, organic titanium modified bisphenol A type epoxy resin, glycidyl amine type epoxy resin and aliphatic epoxidized olefin compound;
the environment-friendly flame-retardant filler is prepared by mixing a phosphorus flame retardant and an inorganic salt flame retardant in a proportion of 1: (1-3), wherein the phosphorus flame retardant is one or more of ammonium polyphosphate, hypophosphite, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, triphenyl phosphorus oxide, diethyl aluminum hypophosphite and resorcinol bis (2, 6-dimethylphenyl) phosphate; the inorganic salt flame retardant is one or more of aluminum hydroxide, magnesium hydroxide, zinc borate and silicate;
the impact modifier is one or more of chlorinated polyvinyl chloride, ethylene-vinyl acetate copolymer and 4, 5-epoxy tetrahydrophthalic dioctyl ester;
the silane coupling agent is one or more of gamma-glycidyl ether propyl trimethoxy silane, 3-glycidyl ether oxygen propyl triethoxy silane, 3-glycidyl ether oxygen propyl trimethoxy silane and 2- (3, 4-epoxy cyclohexyl) ethyl trimethoxy silane;
the reaction accelerator is one or more of organic urea, N' -diphenylguanidine, N-diethylaniline and 2,4, 6-tris (dimethylaminomethyl) phenol;
the curing agent is one or more of an amino resin crosslinking polycondensation-acrylate polymerization system curing agent, a dicyandiamide latent curing agent and a mixed polyisocyanate curing agent;
the organic solvent is one or more of butanone, acetone, cyclohexane, cyclohexanone, toluene, xylene and N, N-dimethylformamide.
3. A process for the preparation of the adhesive according to claim 1 or 2, characterized in that: the method comprises the following steps:
(a) mixing a fluorine-containing elastomer polymer, epoxy resin and an organic solvent of the component A according to a formula amount, stirring at a constant temperature, adding a silane coupling agent according to the formula amount, and stirring at a reduced speed for 40-60 min to obtain a main agent of the component A;
(b) preparing an environment-friendly flame-retardant filler, adding an impact modifier and the environment-friendly flame-retardant filler into a component A main agent according to the formula amount, stirring for 60-90 min at the rotating speed of 1000-3000 rpm, adding a reaction promoter according to the formula amount after uniformly stirring, and stirring for 10-15 min at the rotating speed of 1000-3000 rpm to obtain a component A;
(c) mixing and dissolving a curing agent and an organic solvent of the component B according to the formula amount to obtain the component B;
(d) and mixing the component A and the component B according to a proportion, stirring for 30-40 min, and sieving to obtain the adhesive.
4. The method for preparing the adhesive according to claim 3, which is characterized in that: in the step (a), the parameters of the constant-temperature stirring treatment are as follows: the temperature is one of 60-80 ℃, the rotating speed is 1000-1500 rpm, the time is 4h, the temperature of the constant-temperature stirring treatment is kept in the adding process of the silane coupling agent, and the rotating speed of the speed reduction stirring is 500-800 rpm.
5. The method for preparing the adhesive according to claim 3, which is characterized in that: the stirring speed of the step (d) is 800-1500 rpm, and the sieving mesh number is 300-400 meshes.
6. A flexible copper clad laminate using the adhesive of claim 1 or 2, characterized in that: the adhesive comprises a substrate layer, an adhesive layer and a copper foil layer, wherein the adhesive layer is formed by coating an adhesive, and the adhesive layer is used for bonding the substrate layer and the copper foil layer together.
7. The flexible copper-clad plate using adhesive according to claim 6, wherein: the substrate layer is a biaxially oriented substrate film, and the substrate film is one of a PI film, a PEFT film, a PEN film and an Aramid film; the copper foil layer is electrolytic copper foil or rolled copper foil;
the thickness of the substrate layer is 15-110 μm; the thickness of the bonding layer is 5-70 μm; the thickness of the copper foil layer is 12-150 mu m.
8. The preparation method of the flexible copper-clad plate using the adhesive according to claim 7 is characterized by comprising the following steps: the method comprises the following steps:
(1) performing corona treatment on the surface of the base material layer;
(2) carrying out chemical cleaning and mechanical grinding treatment on the surface of the copper foil layer to enable the surface of the copper foil layer to be provided with a rough surface, so as to obtain a pretreated copper foil layer;
(3) coating an adhesive on the corona treatment surface of the substrate layer to enable the substrate layer to be provided with an adhesive layer, and drying to obtain the adhesive substrate layer;
(4) bonding the bonding surface of the bonding base material layer with the rough surface of the pretreated copper foil layer, carrying out normal-temperature roller pre-lamination, and then carrying out high-temperature hot roller lamination, wherein the temperature of the high-temperature hot roller lamination is set to be 110-150 ℃, so as to obtain a semi-finished product of the flexible copper-clad plate;
(5) and (4) after the soft copper-clad plate semi-finished product is unwound, performing staged curing treatment to obtain a soft copper-clad plate finished product.
9. The preparation method of the flexible copper-clad plate according to claim 8, which is characterized in that: the corona value set in the corona treatment of the step (1) is greater than 52 dy; the speed of coating the adhesive in the step (3) is 2-10 m/min, and the temperature of drying treatment is 140-220 ℃.
10. The preparation method of the flexible copper-clad plate according to claim 8, which is characterized in that: the step-type curing treatment in the step (5): the temperature is increased from 30 ℃ to 100 ℃ in 100min in the first stage; the second stage is to keep the temperature at 100 ℃ within 120 min; in the third stage, the temperature is increased from 100 ℃ to 150 ℃ within 180 min; the fourth stage is to maintain the temperature at 150 ℃ within 120 min; in the fifth stage, the temperature is increased from 150 ℃ to 180 ℃ within 120 min; the temperature dropped from 180 ℃ to 30 ℃ in the sixth stage within 60 min.
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